Naphtholactam dyes

ABSTRACT

Condensation products of derivatives of naphtholactam and barbituric acid useful as dyes for synthetic fibers, particularly synthetic linear polyesters, and for coloring resins. The dyes give brilliant yellow to violet shades having outstanding fastness properties.

This is a division of application Ser. No. 574,401 filed May 5, 1975, now U.S. Pat. No. 4,009,165.

The invention relates to dyes of the formula (I): ##STR1## in which R¹ is hydrogen, chloro, bromo, alkyl, alkoxy, nitro or arylmercapto;

R² is hydrogen or chloro;

R³ is hydrogen, chloro, bromo, alkyl, alkoxy, nitro, carboxylic acylamino, alkylsulfonylamino, arylsulfonylamino, alkylmercapto, arylmercapto, arylsulfonyl, alkylsulfonyl, unsubstituted or substituted sulfamoyl, alkanoyl or aroyl;

R⁴ is hydrogen, chloro, alkoxy or arylmercapto; or

R³ and R⁴ together form a radical of the formula: ##STR2## R⁵ is hydrogen, chloro or alkoxy; and R⁶ and R⁷ independently of one another are alkyl; alkyl bearing hydroxy, cyano, alkoxy or carbalkoxy as a substituent; phenyl; or phenyl bearing chloro, methyl or methoxy as a substituent, at least one of R¹ to R⁵ being different from hydrogen.

Interpretations of R¹ and R^(5:)

Examples of alkyl, alkoxy and arylmercapto groups for R¹ are methyl, ethyl, methoxy, ethoxy, phenylmercapto or phenylmercapto bearing chloro, methyl, methoxy, phenyl, phenoxy or methoxycarbonyl as a substituent.

Examples for R³ are the same radicals as for R¹ and also naphthylmercapto, acetylaminophenylmercapto, acetylamino, propionylamino, benzoylamino, benzoylamino bearing chloro, methyl or methoxy as a substituent, methylsulfonylamino, ethylsulfonylamino, phenylsulfonylamino, tolylsulfonylamino, methylmercapto, β-hydroxyethylmercapto, methylsulfonyl, ethylsulfonyl, phenylsulfonyl, tolylsulfonyl, chlorophenylsulfonyl, acetyl, propionyl, butyryl, benzoyl, benzoyl bearing methyl, methoxy, chloro or bromo as a substituent, sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N-butylsulfamoyl, N-phenylsulfamoyl, N-chlorophenylsulfamoyl, N-methylphenylsulfamoyl, N-methoxyphenylsulfamoyl, N-trifluoromethylphenylsulfamoyl, N-methyl-N-phenylsulfamoyl, N,N-dimethylsulfamoyl, N,N-diethylsulfamoyl, N,N-dipropylsulfamoyl, N,N-dibutylsulfamoyl, pyrrolidinosulfonyl, piperidinosulfonyl or morpholinosulfonyl. Radicals of the formulae: NHCONH₂, NHCONHCH₃ and NHCONHC₆ H₅ are also suitable, Examples of radicals R⁴ are hydrogen, chloro and the alkoxy and arylmercapto radicals specified for R¹.

Examples of alkoxy radicals R⁵ are methoxy and ethoxy.

Particular examples of R⁶ and R⁷ are alkyl of one to four carbon atoms, alkoxyalkyl of three to eight carbon atoms, hydroxyalkyl of two or three carbon atoms, cyanoethyl, alkoxycarbonylalkyl of one to four carbon atoms in the alkoxy and also phenyl.

Specific examples are: propyl, butyl, methoxyethyl, ethoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl, pentoxpropyl, β-hydroxy-ethyl, β-hydroxypropyl, methoxycarbonylethyl, ethoxycarbonylethyl and butoxycarbonylethyl and preferably methyl, ethyl and phenyl.

Dyes of the formula (I) may be prepared by reacting a naphtholactem of the formula (II): ##STR3## or a derivative of the same in which the grouping HN--C═O is replaced by ##STR4## with an N,N'-disubstituted barbituric acid derivative of the formula (III) ##STR5##

Compounds of the formula (II) are known from the literature or may be prepared by methods analogous to those described in the literature.

The reaction of the naphtholactams with the compounds of formula (III) proceeds in the presence of a condensing agent; when the said naptholactam derivatives are used the presence of a condensing agent may be dispensed with.

Phosphorus halides such as phosphorus pentachloride, phosphorus trichloride or phosphorus oxytribromide and particularly phosphorus oxytrichloride are suitable as condensing agents.

The reaction may be carried out in an inert solvent such as toluene, chlorobenzene, dichlorobenzene, nitrobenzene or dioxane or also in an excess of the condensing agent.

When the reaction is carried out with a naphtholactam derivative and without a condensing agent the abovementioned solvents are again suitable; examples of additional solvents are pyridine, glacial acetic acid, dimethylformamide and N-methylpyrrolidone.

The reactions are known in principle and details may be taken from the Examples in which parts and percentages are by weight.

The invention relates particularly to dyes of the formula: ##STR6## in which R¹ is hydrogen, chloro, bromo, C₁ to C₄ alkyl, methoxy, ethoxy, nitro, phenylmercapto or phenylmercapto bearing chloro, methyl or methoxy as a substituent;

R² is hydrogen or chloro;

R³ is chloro, bromo, C₁ to C₄ alkyl, methoxy, ethoxy, nitro, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino, phenylsulfonylamino, tolylsulfonylamino, methylmercapto, ethylmercapto, phenylmercapto, phenylmercapto bearing chloro, methyl or methoxy as a substituent, naphthylmercapto, phenylsulfonyl, phenylsulfonyl bearing chloro or methyl as a substituent, methylsulfonyl, ethylsulfonyl, N-mono-C₁ -to-C₈ -alkyl-substituted sulfamoyl, N,N-di-C₁ -to-C₈ -alkyl-substituted sulfamoyl, N-phenylsulfamoyl, N-chlorophenylsulfamoyl, N-methylphenylsulfamoyl, N-methoxyphenylsulfamoyl, N-trifluoromethylphenylsulfamoyl, sulfopyrrodide, sulfopiperidide, sulfomorpholide, C₂ to C₄ alkanoyl,benzoyl, or benzoyl bearing chloro, bromo, methyl, ethyl, methoxy or ethoxy as a substituent;

R⁴ is hydrogen, chloro, methoxy, ethoxy, phenylmercapto, or phenylmercapto bearing chloro, methyl or methoxy as a substituent; R³ and R⁴ together may be ##STR7## R⁵ is hydrogen, chloro, methoxy or ethoxy; and R⁶ and R⁷ are independently C₁ to C₈ alkyl, C₂ to C₈ alkyl bearing hydroxy, cyano, C₁ to C₄ alkoxy or C₁ to C₄ alkoxycarbonyl as a substituent, phenyl, or phenyl bearing chloro, methyl or methoxy as a substituent. Particular industrial importance attaches to dyes of formula (Ia): ##STR8## in which B¹ is hydrogen, chloro, bromo or arylmercapto;

B² is hydrogen, chloro, bromo, arylmercapto, arylsulfonyl, or aroyl; and

B³ and B⁴ are independently methyl, ethyl or phenyl, methyl being particularly preferred.

The following are preferred arylmercapto, arylsulfonyl and aroyl radicals: phenylmercapto, phenylmercapto bearing chloro, methyl or methoxy as a substituent, phenylsulfonyl or benzoyl, or benzoyl or phenylsulfonyl bearing chloro or methyl as a substituent.

Dyes of formula (I) are yellow to violet and have high brilliance and color strength. They are suitable for dyeing synthetic fibers, particularly polyester fibers, and dyeings having very good fastness properties and particularly excellent fastness to light are obtained. Thermal resistance properties may be influenced by the choice of substituents. Dyes which sublime easily are very suitable for transfer printing.

The new dyes are moreover eminently suitable for the mass coloration of plastics; fluorescent coloration having high fastness to light are obtained as a rule.

The following Examples illustrate the invention.

EXAMPLE 1

200 parts of phosphorus oxychloride is dripped into a mixture of 309 parts of 4-phenylsulfonylnaphtholactam, 165 parts of N,N'-dimethylbarbituric acid and 1200 parts by volume of toluene at 90° C. The whole is stirred for 6 hours at 100° C and 1200 parts by volume of methanol is added during cooling so that the dye is deposited in the form of brown crystals. After cooling, the dye is filtered off, washed with methanol and dried. 357 parts of the dye of the constitution. ##STR9## is obtained which dyes polyester from an aqueous liquor brilliant yellow hues of high tinctorial strength and very good lightfastness and thermal stability.

EXAMPLE 2

The procedure of Example 1 is followed, but the N,N'-dimethylbarbituric acid is replaced by an equivalent amount of N-methyl-N-phenylbarbituric acid. 427 parts of the dye of the constitution ##STR10## is obtained which dyes polyester fast golden yellow hues.

EXAMPLE 3

273 parts of 4-benzoylnaphtholactam-(1,8) and 190 parts of N,N'-dimethylbarbituric acid are introduced into 1000 parts by volume of toluene and stirred at 95° C. 300 parts of phosphorus oxychloride is dripped in within 30 minutes so that the starting materials pass into solution. The whole is stirred for 4 hours at 100° C and during cooling 2000 parts by volume of methanol is allowed to flow in. After suction filtration, washing with methanol and drying there is obtained 360 parts of the dye having the constitution: ##STR11## in the form of yellowish brown crystals. The dye dyes polyester brilliant greenish yellow shades from an aqueous liquor; the dyeings have very good fastness to dry-heat pleating and setting and to light. In thermoplastics such as polystyrene fluorescent yellow hues having outstanding stability at high temperatures and outstanding fastness to light are obtained.

EXAMPLE 4

250 parts of phosphorus oxychloride is added at 100° C within 1 hour to a mixture of 277 parts of 4-phenylmercaptonaphtholactam-(1,8), 190 parts of N,N'-dimethylbarbituric acid and 900 parts by volume of chlorobenzene. The whole is stirred for another 4 hours at 100° C and during cooling there is added a solution of 150 parts of triethylamine in 1500 parts by volume of ethanol. After suction filtration, washing with ethanol and drying there is obtained 349 parts of the dye of the constitution: ##STR12## in the form of a dark red crystalline powder. Brilliant scarlet dyeings and prints of a high level of fastness properties are obtained on polyesters. Thermoplastics such as polystyrene for example are colored fluorescent scarlet shades having excellent stability at high temperature and excellent fastness to light.

EXAMPLE 5

293 parts of 4-phenylmercaptothionaphtholactam and 160 parts of N,N'-dimethylbarbituric acid are boiled in 400 parts by volume of N-methylpyrrolidone for 8 hours. 200 parts by volume of ethanol is added during cooling. The product is suction filtered, washed and dried. 302 parts of dye is obtained which is identical with that specified in Example 4.

EXAMPLE 6

307 parts of 4-phenylmercapto-thionaphtholactim-S-methyl ether and 160 parts of N,N'-dimethylbarbituric acid are boiled in 600 parts by volume of acetic acid for 1 hour. The dye precipitates in the form of red crystals. Upon working up, 328 parts of dye is obtained which is identical with that specified in Example 4.

EXAMPLE 7

41.3 parts of 2,4-bis-(4-methylphenylmercapto)-naphtholactam-(1,8) and 20 parts of N,N'-diethylbarbituric acid are introduced into 150 parts by volume of dichlorobenzene and stirred at 95° C. 30 parts of phosphorus oxychloride is dripped in so that the components pass into solution. The whole is stirred for 6 hours at 95° C, diluted with 300 parts by volume of methanol and allowed to cool while stirring. The red crystals are suction filtered, washed with methanol and dried. 49.2 parts of the dye of the constitution: ##STR13## is obtained which gives in polystyrene bluish red hues of outstanding stability at high temperatures and outstanding fastness to light.

EXAMPLE 8

268 parts of the compound of the formula ##STR14## (prepared by the method of German Laid-Open Specification No. 1,445,624, Example 2) is heated for 30 minutes at 100° to 120° C in 1,000 parts of xylene. 220 parts of N-methyl-N'-(3-methoxypropyl)-barbituric acid is added and heating is continued at 100° C for 120 minutes. During cooling, 500 parts of methanol is added and the dye isolated in the usual manner. 311 parts of the dye of the constitution ##STR15## is obtained in the form of orange crystals, which dye polyester reddish yellow hues having very good lightfastness.

The following dyes of the general formula (I) are prepared according to the methods specified in Examples 1 to 8.

    __________________________________________________________________________     Ex.                                                                               R.sup.1 R.sup.2                                                                          R.sup.3    R.sup.4 R.sup.5                                                                             R.sup.6                                                                             R.sup.7 Hue                          __________________________________________________________________________      9 --C.sub.2 H.sub.5                                                                      H H          H       H    --CH.sub.3                                                                          --CH.sub.3                                                                             greenish                                                                       yellow                       10 H       " --CH.sub.3 "       "    "    "       "                            11 "       " Cl         "       "    "    "       reddish                                                                        yellow                       12 "       " "          "       "    "    --C.sub.6 H.sub.5                                                                      "                            13 "       " "          "       "    --C.sub.6 H.sub.5                                                                   "       "                            14 Cl      " "          "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             "                            15 "       " "          "       "    "    --C.sub.2 H.sub.5                                                                      "                            16 "       H "          "       "    "    --(CH.sub.2).sub.3 OCH.sub.3                                                           "                            17 H       " H          Cl      "    "    --CH.sub.3                                                                             "                            18 "       " Cl         "       "    "    "       orange                                                                         yellow                       19 "       " "          "       "    --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                      "                            20 "       Cl                                                                               "          "       Cl   --CH.sub.3                                                                          --CH.sub.3                                                                             yellowish                                                                      orange                       21 "       " "          "       "    --C.sub.4 H.sub.9                                                                   --C.sub.4 H.sub.9                                                                      "                            22 "       " "          "       "    --CH.sub.3                                                                          --(CH.sub.2).sub.3 OC.sub.2                                                    H.sub.5 "                            23 "       " "          "       "    --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                      "                            24 "       H Br         H       H    --CH.sub.3                                                                          --CH.sub.3                                                                             reddish                                                                        yellow                       25 "       " "          "       "    "    --C.sub.4 H.sub.9                                                                      "                            26 "       " "          "       "    "    --(CH.sub. 2).sub.3 OCH.sub.3                                                          "                            27 "       " "          "       "    --C.sub.6 H.sub.5                                                                   --C.sub.6 H.sub.5                                                                      "                            28 Br      " Cl         "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             "                            29 Cl      " Br         "       "    "    "       "                            30 Br      " "          "       "    "    "       yellowish                                                                      orange                       31 "       " "          "       "    "    --(CH.sub.2).sub.3 OCH.sub.3                                                           "                            32 "       " "          "       "    "    --(CH.sub.2).sub.3 OC.sub.2                                                    H.sub.5 "                            33 "       " "          "       "    --C.sub.4 H.sub.9                                                                   --C.sub.4 H.sub.9                                                                      "                            34 "       " "          "       "    --C.sub.6 H.sub.5                                                                   --C.sub.6 H.sub.5                                                                      "                            35 H       " NO.sub.2   "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             golden                                                                         yellow                       36 "       " "          "       "    --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                      "                            37 NO.sub.2                                                                               " Br         "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             reddish                                                                        yellow                       38 Br      " NO.sub.2   "       "    "    "       golden                                                                         yellow                       39 H       " OCH.sub.3  "       "    "    "       yellow                       40 "       " "          "       "    "    --C.sub.2 H.sub.5                                                                      "                            41 "       " "          "       "    --C.sub.6 H.sub.5                                                                   --C.sub.6 H.sub.5                                                                      "                            42 "       " OC.sub.2 H.sub.5                                                                          "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             "                            43 "       " NHCONH.sub.2                                                                              "       "    "    "       "                            44 "       " "          "       "    --C.sub.6 H.sub.5                                                                   --C.sub.6 H.sub.5                                                                      "                            45 "       " NHCONHCH.sub.3                                                                            "       "    "    "       "                            46 "       " NHCONHC.sub.6 H.sub.5                                                                     "       "    "    "       "                            47 "       " NHCOC.sub.6 H.sub.5                                                                       "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             "                            48 "       " "          "       "    --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                      "                            49 "       " NHSO.sub.2 C.sub.6 H.sub.5                                                                "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             "                            50 "       " NHSO.sub.2 CH.sub.3                                                                       "       "    "    "       "                            51 "       " H          --OCH.sub.3                                                                            "    "    "       "                            52 "       " "          H       --OCH.sub.3                                                                         "    "       "                            53 "       " "          "       --OC.sub.2 H.sub.5                                                                  "    "       "                            53 "       " SCH.sub.3  "       H    "    "       orange                       55 "       " SC.sub.6 H.sub.5                                                                          "       "    "    --C.sub.2 H.sub.5                                                                      yellowish                                                                      red                          56 "       " "          "       "    "    --(CH.sub.2).sub.3 OCH.sub.3                                                           "                            57 "       " "          "       "    --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                      "                            58 "       " "          "       "    --CH.sub.3                                                                          --C.sub.4 H.sub.9                                                                      "                            59 "       " "          "       "    --C.sub.6 H.sub.5                                                                   --C.sub.6 H.sub.5                                                                      "                            60 "       " Cl         SC.sub.6 H.sub.5                                                                       "    --CH.sub.3                                                                          --CH.sub.3                                                                             orange                                                                         yellow                       61 "       " "          "       "    "    --(CH.sub.2).sub.3 OCH.sub.3                                                           "                            62 "       " SC.sub.6 H.sub.4 CH.sub.3 (4)                                                             H       "    "    --CH.sub.3                                                                             red                          63 "       " "          "       "    --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                      "                            64 "       " Cl         SC.sub.6 H.sub.4 CH.sub.3 (4)                                                          "    --CH.sub.3                                                                          --CH.sub.3                                                                             orange                       65 "       " SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                            H       "    "    "       red                          66 "       " "          "       "    "    --C.sub.4 H.sub.9                                                                      "                            67 "       " "          "       "    "    --(CH.sub.2).sub.3 OC.sub.2                                                    H.sub.5 "                            68 "       " Cl         SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                         "    "    --CH.sub.3                                                                             yellowish                                                                      red                          69 "       " SC.sub.6 H.sub.4 Cl(4)                                                                    H       "    "    "       orange                       70 "       " "          "       "    "    --C.sub.4 H.sub.9                                                                      "                            71 "       " SC.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                           "       "    "    --CH.sub.3                                                                             yellowish                                                                      orange                       72 "       " SC.sub.6 H.sub.4 C.sub.6 H.sub.5 (4)                                                      "       "    "    "       red                          73 "       " SC.sub.6 H.sub.4 OC.sub.6 H.sub.5 (4)                                                     "       "    "    "       "                            74 "       " SC.sub.6 H.sub.4 NHCOCH.sub.3 (4)                                                         "       "    "    "       yellowish                                                                      red                          75 "       " SC.sub.6 H.sub.4 COOCH.sub.3 (4)                                                          "       "    "    "       red                          76 "       " Naphthyl-2-S-                                                                             "       "    "    "       "                            77 "       " "          "       "    --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                      "                            78 SC.sub.6 H.sub.5                                                                       " Cl         "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             orange                       79 "       " "          "       "    "    --C.sub.4 H.sub.9                                                                      "                            80 "       " NO.sub.2   "       "    "    --CH.sub.3                                                                             "                            81 "       " SC.sub.6 H.sub.5                                                                          "       "    "    "       reddish                                                                        orange                       82 "       " "          "       "    --C.sub.4 H.sub.9                                                                   --C.sub.4 H.sub.9                                                                      "                            83 "       " "          "       "    --CH.sub.3                                                                          --(CH.sub.2).sub.3 OC.sub.2                                                    H.sub.5 "                            84 "       " "          "       "    --C.sub.6 H.sub.5                                                                   --C.sub.6 H.sub.5                                                                      "                            85 H       " "          SC.sub.6 H.sub.5                                                                       "    --CH.sub.3                                                                          --CH.sub.3                                                                             yellowish                                                                      red                          86 "       " "          "       "    "    --C.sub.4 H.sub.9                                                                      "                            87 SC.sub.6 H.sub.4 CH.sub.3 (4)                                                          " SC.sub.6 H.sub.4 CH.sub.3 (4)                                                             H       "    "    --CH.sub.3                                                                             red                          88 "       " "          "       "    "    --(CH.sub.2).sub.3 OCH.sub.3                                                           "                            89 "       " "          "       "    --C.sub.4 H.sub.9                                                                   --C.sub.4 H.sub.9                                                                      "                            90 SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                         " SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                            "       "    --CH.sub.3                                                                          --CH.sub.3                                                                             bluish                                                                         red                          91 "       " "          "       "    --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                      "                            92 H       " "          SC.sub.6 H.sub.4 OCH.sub.3 (4)                                                         "    -- CH.sub.3                                                                         --CH.sub.3                                                                             yellowish                                                                      red                          93 SC.sub.6 H.sub.4 Cl(4)                                                                 " SC.sub.6 H.sub.4 Cl(4)                                                                    H       "    "    "       reddish                                                                        orange                       94 "       " "          "       "    "    --C.sub.4 H.sub.9                                                                      "                            95 SC.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                        " SC.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                           "       "    "    --CH.sub.3                                                                             orange                       __________________________________________________________________________

EXAMPLE 96

200 parts of N,N'-dimethylbarbituric acid and 275 parts of the compound of the constitution: ##STR16## are brought into solution in 1800 parts by volume of anhydrous nitrobenzene by heating 220 parts of phosphorus oxychloride is dripped in at 100° C and the whole is stirred for another 12 hours at 100° C. After cooling it is diluted with an equal volume of ethanol, suction filtered, washed with ethanol and dried. 321 parts of the dye of the formula: ##STR17## is obtained in the form of a dark crystalline powder. When the dye is incorporated into polystyrene it gives violet hues having good stability to high temperature and good lightfastness properties.

When the N,N-dimethylbarbituric acid is replaced by barbituric acids having other substituents, dyes having very similar hues are obtained.

Other dyes of the constitution (I) which are obtained analogously to Examples 1 to 8 , are:

    __________________________________________________________________________     Ex.                                                                               R.sup.3 (R.sup.1 =R.sup.2 =R.sup.4 =R.sup.5 =H)                                             R.sup.6                                                                             R.sup.7  Hue                                              __________________________________________________________________________      97                                                                               SO.sub.2 C.sub.6 H.sub.5                                                                    CH.sub.3                                                                            C.sub.4 H.sub.9                                                                         golden yellow                                     98                                                                               "            "    (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                       "                                                 99                                                                               "            C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9                                                                         "                                                100                                                                               SO.sub.2 C.sub.6 H.sub.4 CH.sub.3 (4)                                                       CH.sub.3                                                                            CH.sub.3 "                                                101                                                                               "            "    C.sub.2 H.sub.5                                                                         "                                                102                                                                               "            C.sub.6 H.sub.5                                                                     C.sub.6 H.sub.5                                                                         "                                                103                                                                               SO.sub.2 C.sub.6 H.sub.4 Cl                                                                 CH.sub.3                                                                            CH.sub.3 "                                                104                                                                               "            C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         "                                                105                                                                               "            CH.sub.3                                                                            C.sub.4 H.sub.9                                                                         "                                                106                                                                               "            C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9                                                                         "                                                107                                                                               SO.sub.2 N)CH.sub.3).sub.2                                                                   CH.sub.3                                                                           CH.sub.3 yellow                                           108                                                                               SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                           "    "        "                                                109                                                                               SO.sub.2 N(C.sub.4 H.sub.9).sub.2                                                           "    "        "                                                110                                                                                ##STR18##   "    "        "                                                111                                                                               "            "    C.sub.2 H.sub.5                                                                         "                                                112                                                                                ##STR19##   "    CH.sub.3 "                                                113                                                                                ##STR20##   C.sub.4 H.sub.9                                                                     C.sub.4 H.sub.9                                                                         "                                                114                                                                               SO.sub.2 NHC.sub.6 H.sub.5                                                                  CH.sub.3                                                                            CH.sub.3 "                                                115                                                                               SO.sub.2 NHC.sub.6 H.sub.4 CH.sub.3 (4)                                                     "    "        "                                                116                                                                               SO.sub.2 NHC.sub.6 H.sub.4 Cl(2)                                                            "    "        "                                                117                                                                               SO.sub.2 NHC.sub.6 H.sub.4 OCH.sub.3 (4)                                                    "    "        "                                                118                                                                               SO.sub.2 NHC.sub.6 H.sub.4 CF.sub.3 (3)                                                     "    "        "                                                119                                                                                ##STR21##   "    "        "                                                120                                                                               COCH.sub.3   "    "        greenish yellow                                  121                                                                               COC.sub.3 H.sub.7 (iso)                                                                     C.sub.6 H.sub.5                                                                     C.sub.6 H.sub.5                                                                         "                                                122                                                                               COC.sub.6 H.sub.5                                                                           C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         "                                                123                                                                               "            CH.sub.3                                                                            C.sub.4 H.sub.9                                                                         "                                                124                                                                               "            "    C.sub.6 H.sub.5                                                                         "                                                125                                                                               "            C.sub.6 H.sub.5                                                                     "        "                                                126                                                                               COC.sub.6 H.sub.4 CH.sub.3 (2)                                                              CH.sub.3                                                                            CH.sub.3 yellow                                           127                                                                               COC.sub.6 H.sub.4 CH.sub.3 (4)                                                              "    "        "                                                128                                                                               "            "    C.sub.2 H.sub.5                                                                         "                                                129                                                                               COC.sub.6 H.sub.4 Cl(2)                                                                     "    CH.sub.3 greenish yellow                                  130                                                                               COC.sub.6 H.sub.4 Cl(4)                                                                     CH.sub.3                                                                            CH.sub.3 "                                                131                                                                               "            C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                         "                                                132                                                                               "            CH.sub.3                                                                            (CH.sub.2).sub.3 OCH.sub.3                                                              "                                                133                                                                               COC.sub.6 H.sub. 3 Cl.sub.2 (2,4)                                                           "    CH.sub.3 "                                                134                                                                               "            "    C.sub.4 H.sub.9                                                                         "                                                135                                                                               COC.sub.6 H.sub.3 Cl.sub.2 (3,4)                                                            "    CH.sub.3 "                                                136                                                                               COC.sub.6 H.sub.3 Cl.sub.2 (2,5)                                                            "    "        "                                                137                                                                               "            "    (CH.sub.2).sub.3 OC.sub.2 H.sub.5                                                       "                                                138                                                                               "            C.sub.6 H.sub.5                                                                     C.sub.6 H.sub.5                                                                         "                                                __________________________________________________________________________

example 139

208 parts of N-methyl-N'-butylbarbituric acid and 271 parts of the compound of the constitution: ##STR22## are stirred into 1200 parts by volume of anhydrous trichlcorobenzene at 100° C. 300 parts of phosphorus oxychloride is dripped in within 1 hour and the whole is stirred for another 8 hours at 100° C to 110° C. During cooling the whole is diluted with 800 parts by volume of methanol and then suction filtered, washed and methanol and dried. 361 parts of the dye of the constitution: ##STR23## is obtained in the form of reddish brown crystals. Luminous orange colorations having good fastness properties are obtained with the dye in thermoplastics, as for example polystyrene. 

I claim:
 1. A compound of the formula ##STR24## in which R¹ is hydrogen, chloro, bromo, C₁ to C₄ alkyl, methoxy, ethoxy, nitro, phenylmercapto, or phenylmercapto substituted by chloro, methyl or methoxy,R² is hydrogen or chloro, R³ is chloro, bromo, C₁ -C₄ -alkyl, methoxy, ethoxy, nitro, acetylamino, propionylamino, benzoylamino, methylsulfonylamino, ethylsulfonylamino, phenylsulfonylamino, tolylsulfonylamino, methylmercapto, ethylmercapto, phenylmercapto, phenylmercapto substituted by chloro, methyl or methoxy, napthylmercapto, phenylsulfonyl, phenylsulfonyl substituted by chloro or methyl, methylsulfonyl, ethylsulfonyl, N-mono-C₁ - to C₈ -alkyl-substituted sulfamoy, N,N-di-C₁ - to C₄ -alkyl-substituted sulfamoyl, N-phenylsulfamoyl, N-chloro-, -methyl-, -methoxy- or trifluoromethylphenylsulfamoyl, sulfopyrrolidide, sulfo-piperidide, sulfomorpholide, C₂ - to C₄ -alkanoyl, benzoyl or benzoyl substituted by chloro, bromo, methyl, ethyl, methoxy, or ethoxy, R⁴ is hydrogen, chloro, methoxy, ethoxy phenylmercapto, or phenylmercapto substituted by chloro, methyl or methoxy, or R³ and R⁴ together are ##STR25## R⁵ is hydrogen or chloro, methoxy or ethoxy, and R⁶ and R⁷ are independently C₁ - to C₈ -alkyl, C₂ - to C₈ -alkyl substituted by hydroxy, cyano, C₁ - to C₄ -alkoxy or C₁ - to C₄ -alkoxy-carbonyl, phenyl, or phenyl substituted by chloro, methyl or methoxy with the proviso that at least one of the substituents R¹, R³ or R⁴ contains a sulfur atom.
 2. A compound according to the formula in claim 1, wherein R², R⁴ and R⁵ are hydrogen.
 3. A compound according to the formula in claim 1, wherein R², R⁴ and R⁵ are hydrogen.R¹ is hydrogen, phenylmercapto or phenylmercapto substituted by chloro, methyl or methoxy and R³ is phenylmercapto or phenylmercapto substituted by chloro, methyl or methoxy.
 4. A compound according to the formula in claim 1, wherein R¹, R², R⁴ and R⁵ are hydrogen andR³ is phenylsulfonyl or phenylsulfonyl substituted by chloro or methyl.
 5. A compound according to claim 1 of the formula ##STR26## in which R³ is phenylmercapto, phenylmercapto substituted by chloro, methyl or methoxy, phenylsulfonyl or phenylsulfonyl substituted by chloro or methyl, andR⁶ and R⁷ are methyl or ethyl.
 6. The compound according to claim 1 of the formula ##STR27##
 7. The compound according to claim 1 of the formula ##STR28##
 8. The compound according to claim 1 of the formula ##STR29## 